Polyelectrolyte-layer forming block copolymers and compositions and uses thereof

ABSTRACT

The present invention relates generally to polyelectrolyte-layer forming block copolymers adsorbed at colloid interfaces in aqua solution and compositions and uses thereof. In particular, the present invention relates to agricultural material compositions comprising particles of at least one agricultural material and a polyelectrolyte-layer forming block copolymer. The present invention also relates to non-agricultural material compositions comprising particles of at least one non-agricultural material and a polyelectrolyte-layer forming block co-polymer.

This application claims priority of U.S. Provisional Application No.62/265,725, filed Dec. 10, 2015, the entire content of which is herebyincorporated by reference herein.

The present invention relates generally to polyelectrolyte-layer formingblock copolymers adsorbed at colloid interfaces in aqua solution andcompositions and uses thereof. In particular, the present inventionrelates to agricultural material compositions comprising particles of atleast one agricultural material compound and a polyelectrolyte-layerforming block copolymer. The present invention also relates tonon-agricultural material compositions comprising particles of at leastone non-agricultural material compound and a polyelectrolyte-layerforming block co-polymer.

BACKGROUND

Forces between particles and drops influence the properties of acomposition, the preparation and application thereof. For example, inliquid dispersions or suspension, when concentration of the particles isincreased, the friction between the particles and accordingly theviscosity of the formulation typically increases as well. In emulsions,increasing the amount of the dispersed phase in the continuous phasemight lead to an inversion of phases, resulting in an inverse emulsion.

Forces between particles can also significantly affect milling andgranulation processes. At high particle concentrations, the viscosityand temperature of a liquid suspension will typically increase duringmilling, and the process will become inefficient or destructive to theactive ingredient. In the granulation process, where the concentrationsof solids are high, reducing the pressure is necessary for producingproper granules.

Many pesticidal active ingredients (AI) and other materials foragricultural application are hydrophobic and insoluble in water.Therefore, water based formulations are composed of the hydrophobicsolid particles of the AI suspended in the aqua phase or hydrophobicdrops and capsules, which contain the active ingredient, dispersed inthe water.

Further, the concentration of a pesticide active material and othermaterials for agricultural application in a formulation can influencethe application rate and packaging of the product. High-loadformulations require less packaging and thus are easier to handle andtransport. In many cases the ultimate goal for designing a pesticidalformulation is to prepare the formulation with the highest possibleamount of the active material, with the resultant formulationmaintaining stability and a long shelf life, and also providing anenvironmentally friendly and cheaper product.

Various dispersing agents and surfactants are known in the art toachieve these purposes. The dispersing agents in this regard can beionic or non-ionic compounds, polymeric or non-polymeric surfactants.Some of these co-formulants impart rheology properties for theconcentrated pesticidal formulations. The dispersant surrounds theparticles and disperses the particles in the liquid phase and thereforeprevents and/or breaks aggregates.

Previously exemplified and known dispersants useful in this regardinclude comb co-polymers such as Atlox™ 4913, block co-polymers ofalkylene oxide, ethoxylate alcohol and anionic type polymers such asfatty acid sulfonate.

In order to achieve and stabilize a high load formulation there is aneed for the dispersants to stabilize extremely well againstflocculation and coagulation, to perform well at low concentration ofdispersant and to reduce the friction between the particles. Ingranulation processes, good lubricating properties of the dispersant arealso desired. Another important property for a dispersant is goodperformance in both high and low concentrations of the electrolyte.

Many polyelectrolytes are known in the art. For example, WO 2015116716is directed to compositions for plant growth regulation comprising atleast one polyanionic polymer in combination with one or more plantgrowth regulators, in preferred forms, the polyanionic polymer comprisesa copolymer polymers having repeat units randomly located along thepolymer chain without any ordered sequence of repeat units.

WO 2013004704 discloses, in part, an apolar liquid comprising micellescomprising a copolymer AB, in which the micellar cores are morehydrophilic than the micelle coronas. The copolymer is formed asmicelles in a water-free organic solvent liquid medium to provide asurface coating.

WO 2013189776 discloses a solid dispersion consisting of hydrophobicactive ingredients and cationic copolymers of N,N-diethylaminoethylmethacrylate and methyl methacrylate, the monomers being provided at aweight ratio of 35:65 to 55:45.

WO 2013133706 discloses compositions comprising a polyelectrolytecomplex of a polyanion, preferably selected from the group consisting ofa natural polyanion such as xanthan gum, alginate, a lignin compoundsuch as lignosulfonate, pectin, carrageenan, humic acid, fulvic acid,angico gum, gum Kondagogu, sodium alkyl naphtalene sulfonate,poly-γ-glutamic acid, maleic starch half-ester, carboxymethyl cellulose,chondroitin sulphate, dextran sulphate, hyaluronic acid, and a syntheticpolyanion such as poly(acrylic acid), polyphosphoric acid, andpoly(L-lactide), and a polycation preferably selected from the groupconsisting of poly-L-lysine, epsilon-poly-L-lysine, poly-L-arginine,chitosan oligosaccharide and chitosan.

WO 2013093578 discloses a polymer selected from the group consisting ofpoly(methacrylic acid-co-ethyl acrylate); poly(methacrylicacid-co-styrene); poly(methacrylic acid-co-butylmethacrylate);poly[acrylic acid-co-poly(ethylene glycol) methyl ether methacrylate];and poly(n-butylmethacrylcate-co-methacrylic acid).

Any known dispersants as described by the prior art are limited in someof the characteristics needed for a dispersant to achieve a high loadformulation: stabilization against agglomeration, reduction in thefriction between particles, perform well at low concentration andefficient in different electrolyte solutions. Thus, the prior arttypically provides products with the amount of particles present beinglimited. Accordingly, there remains a need in the art for pesticidalcompositions containing improved dispersants which permit a higherconcentration of the active ingredient in the composition, and whichenable improved milling and granulation of the composition.

SUMMARY OF THE PRESENT SUBJECT MATTER

Generally, the present subject matter relates to the use of apolyelectrolyte-layer forming block copolymer as a dispersant oremulsifier wherein the block copolymers adsorb on the surfaces of theactive ingredient particles in a dispersion to result in a stablebrushed “particle-polymer” complex. Accordingly, the presentcompositions have a reduced friction between particles and stabilizedispersions in a very efficient way. Also, by combining steric and ionicstabilization they perform well at both high and low concentrations ofelectrolytes.

The subject invention provides an agricultural material compositioncomprising:

-   -   (i) particles of at least one agricultural material compound;        and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the agricultural material compound particles.

The subject invention provides a pesticidal composition comprising:

-   -   (i) particles of at least one pesticide compound; and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the pesticide compound particles.

The subject invention also provides a method of controlling andpreventing pest comprising applying a pesticidal composition to a locuswhere the pest is to be controlled and prevented, wherein the pesticidalcomposition comprises:

-   -   (i) particles of at least one pesticide compound; and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the pesticide compound particles.

The subject invention also provides a method of improving plant growthcomprising applying an agricultural material composition to at least oneof a plant, an area adjacent to a plant, soil adapted to support growthof a plant, a root of a plant, foliage of a plant, and/or a seed adaptedto produce a plant, wherein the composition comprises:

-   -   (i) particles of at least one agricultural material; and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the agricultural material particles.

The subject invention also provides a process of preparing a compositioncomprising mixing particles of at least one compound with an amount of apolyelectrolyte-layer forming block co-polymer, wherein the blockcopolymer comprises (A) an anchoring moiety and (B) at least onestabilizing moiety.

The subject invention also provides a process of preparing a pesticidalcomposition comprising mixing particles of at least one pesticidecompound with an amount of a polyelectrolyte-layer forming blockco-polymer, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety.

The subject invention also provides a colorant system compositioncomprising:

-   -   (i) a colorant component; and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the colorant system composition is produced as a        dispersion.

The subject invention also provides an aqueousnon-agricultural-application-based composition comprising at least:

-   -   (i) one non-agricultural material compound;    -   (ii) water; and    -   (iii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety.

The subject invention also provides a method of preparing a coatingcomposition comprising contacting a film forming polymer latex with adispersant system comprising a polyelectrolyte-layer forming blockcopolymer, wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety.

The subject invention also provides a method of preparing a colorantsystem composition comprising contacting a colorant component with adispersant system comprising a polyelectrolyte-layer forming blockcopolymer wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety, and wherein the resultingcolorant system composition is a dispersion.

The subject invention also provides a method of tinting an alkyd-basedbase coating or a latex-based base coating comprising contacting thealkyd-based base coating or the latex-based base coating with a colorantsystem composition, wherein the colorant system composition comprises:

-   -   i) a colorant component; and    -   ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the colorant system composition is prepared as a        dispersion.

The subject invention also provides an oil cement grout compositioncomprising solid particles and a polyelectrolyte-layer forming blockcopolymer wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety.

The subject invention also provides use of a polyelectrolyte-layerforming block copolymer comprising (A) an anchoring moiety and (B) atleast one stabilizing moiety for keeping solid particles in suspensionin an oil cement grout composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the change in the viscosity between the milling steps forformulation 1, without the presently described polymer, and forformulation 2, with the presently described polymer.

FIG. 2 shows the change in the particle size distribution during themilling steps in the production process.

FIGS. 3A and 3B provides a comparison of performances of knowndispersants and of the presently described polymer dispersant in highsalt solutions.

FIG. 4 provides a comparison of performances of additional knowndispersants and of the presently described polymer dispersant in highsalt solutions.

FIGS. 5A and 5B provide a comparison of performances of further knowndispersants and of the presently described polymer dispersant in highsalt solutions.

FIG. 6 shows the viscosities during the milling of Formulation 3 andFormulation 2.

FIG. 7 shows the general structure of a di-block copolymer.

FIG. 8 shows the general structure of a tri-block copolymer.

FIG. 9 shows the general structure of a comb-graft polymer/copolymer.

DETAILED DESCRIPTION OF THE PRESENT SUBJECT MATTER

Prior to setting forth the present subject matter in detail, it may behelpful to provide definitions of certain terms to be used herein.Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this subject matter pertains.

Definitions

As used herein, the term “agricultural material” means an activeingredient used in the practice of farming, including cultivation of thesoil for the growing of crops. However, the use of agriculturalmaterials is not limited to application to crops. Agricultural materialsmay be applied to any surface, e.g., for the purpose of cleaning oraiding or inhibiting growth of a living organism. Other non-cropapplications include, but are not limited to, application to an animal,e.g. livestock, application to turf and ornamentals, and application torailroad weed.

As used herein, the term “agrochemical” is a chemical active ingredientused in the practice of farming, including cultivation of the soil forthe growing of crops. However, the use of agrochemicals is not limitedto application to crops. Agrochemicals may be applied to any surface,e.g., for the purpose of cleaning or aiding or inhibiting growth of aliving organism.

Examples of agricultural materials and agrochemicals include, but arenot limited to, pesticides, hormones, bio-stimulants, and plant growthagents.

As used herein, the term “pesticide”, “pesticide compound” or“pesticidal compound” means a compound capable of killing or inhibitinggrowth or proliferation of a pest, whether for plant protection or fornon-crop application. As used herein, all “pesticide”, “pesticidecompound” or “pesticidal compound” fall within “agricultural materialcompound”. The term “pesticide”, “pesticide compound” or “pesticidalcompound” includes, but is not limited to, insecticide, nematicide,herbicide, fungicide, algicides, animal repellents, and acaricides. Asused herein, the term “pest” includes, but is not limited to, insect,nematode, weed, fungi, algae, mite, tick, and animal. As used herein,the term “weed” refers to any unwanted vegetation.

As used herein, the term “hydrophobic” when used to characterize acompound or a surface means that the compound or surface lacks affinityfor water.

As used herein, the term “polyelectrolyte” means a polymer whichcontains charged monomers.

As used herein, the phrase “block copolymer” means a polymer comprisingat least two different polymers combined by a covalent bond. Each of theblocks is usually a homopolymer but can also be a copolymer with aspecific distinct physical/chemical or functional characteristic (e.g.,having one block that is easily soluble in water, with the other blockbeing primarily insoluble in water).

As used herein, the phrase “anchoring block”, “anchoring moiety” or“ANCHOR” means a block comprised of a homopolymer or copolymer which hasan affinity for the particle surface and which will cause the blockcopolymer to adsorb strongly and even irreversibly to the particlesurface.

As used herein, the phrase “stabilizing block”, “stabilizing moiety” or“STAB” means a charged polymer zone for which the dispersing medium, ex.water, is a good solvent. More specifically, if a copolymer is preparedof same molar mass and composition as that of the stabilizing block,then it should be soluble in the dispersing medium at a concentrationgreater than or equal to 10 wt %, for instance greater than or equal to20 wt %, for instance greater than or equal to 30 wt %, for instancegreater than or equal to 40 wt %, for instance greater than or equal to50 wt %, for instance greater than or equal to 60 wt % and even 80 wt %.

As used herein, the phrase “comb copolymer” means polymers wherein sidepolymeric chains are bonded to a polymer/copolymeric main chain,frequently also known as the backbone. In the present case, the presentpolymer/copolymers have at least one repeat unit derived frompolyolefin-based macromonomers.

As used herein, the term “dispersion” means a formulation which includesa heterogeneous mixture of at least two phases wherein the first(continuous phase) is liquid and the second (dispersed phase) is solidor liquid particles. The “dispersion” compositions discussed hereinnecessarily include an aqueous phase as the continuous phase.

As used herein, the term “suspension” and “dispersion” areinterchangeable and means a formulation having solid particles that aremixed with at least one liquid phase but which remain undissolved. Wateris the continuous phase.

As used herein, the phrase “capsule suspension” means a formulationhaving solid capsules contained active ingredient, surrounding by asolid coating, dispersed in water.

As used herein, the terms “particle”, “solid particle”, “liquiddroplets” and capsules can be used interchangeably to mean solids and/ordrops.

As used herein, particles having a “brushed structure” have a layer ofpolymers attached on one end to the surface of the particles and on theother end extend normal to the surface into a bulk solution.

As used herein, the phrase “agriculturally acceptable carrier” meanscarriers, which are known and accepted in the art for the formation offormulations for agricultural or horticultural use.

As used herein, the phrase “ultra-high concentration” and “high-loadconcentration” means active substances in amounts of at least 500 g/L.

The term “a” or “an” as used herein includes the singular and theplural, unless specifically stated otherwise. Therefore, the terms “a,”“an” or “at least one” can be used interchangeably in this application.

Throughout the application, descriptions of various embodiments use theterm “comprising”; however, it will be understood by one of skill in theart, that in some specific instances, an embodiment can alternatively bedescribed using the language “consisting essentially of” or “consistingof.” Throughout this specification and the claims which follow, unlessthe context requires otherwise, the word “comprise”, and variations suchas “comprises” or “comprising”, will be understood to imply theinclusion of a stated integer or step or group of integers or steps butnot the exclusion of any other integer or step or group of integers orsteps.

As used herein, the term “high salt environment” means that thecomposition contains at least 5% by weight of salt relative to theweight of the composition. The composition may also contain at least 7%by weight of salt or at least 10% by weight of salt relative to thetotal weight of the composition.

For purposes of better understanding the present teachings and in no waylimiting the scope of the teachings, unless otherwise indicated, allnumbers expressing quantities, percentages or proportions, and othernumerical values used in the specification and claims, are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained. At the very least, each numerical parametershould at least be construed in light of the number of reportedsignificant digits and by applying ordinary rounding techniques. In thisregard, used of the term “about” herein specifically includes ±10% fromthe indicated values in the range. In addition, the endpoints of allranges directed to the same component/moiety/or property herein areinclusive of the endpoints, are independently combinable, and includeall intermediate points and ranges.

It is understood that where a parameter range is provided, all integerswithin that range, and tenths thereof, are also provided by theinvention.

All publications, patents and patent applications mentioned in thisspecification are herein incorporated in their entirety by referenceinto the specification, to the same extent as if each individualpublication, patent or patent application was specifically andindividually indicated to be incorporated herein by reference.

Agricultural Material Compositions and Uses Thereof

The subject invention provides an agricultural material compositioncomprising:

-   -   (i) particles of at least one agricultural material compound,        and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the agricultural material compound particles.

The subject invention provides a pesticidal composition comprising:

-   -   (i) particles of at least one pesticide compound, and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the pesticide compound particles.

The block copolymer is adsorbed at the interface between the hydrophobicsurface of the particles and the water. When surrounded in a watermedium, the block copolymer hydrates, leading to a highly efficientlubrication. In an embodiment, the particles are dispersed in the water.The resultant particles of the combination of the polyelectrolyte-layerformed through the block copolymer and the active ingredient has abrushed structure. In water, the brushed polyelectrolyte layer ishydrated, resulting in a highly efficient lubrication.

In one embodiment, the composition is a dispersion.

In one embodiment, the agricultural material is an agrochemical.

In one embodiment, the agricultural material is a plant growthregulator. In one embodiment, the agricultural material is abio-stimulant. In one embodiment, the agricultural material is ahormones.

In one embodiment, the agricultural material is a pesticide.

In one embodiment, the pesticide is an insecticide. In one embodiment,the pesticide is a nematicide. In one embodiment, the pesticide is anherbicide. In one embodiment, the pesticide compound is a fungicide. Inone embodiment, the pesticide is an algicide. In one embodiment, thepesticide is an animal repellent. In one embodiment, the pesticide is anacaricide.

Examples of herbicides may include, but are not limited to, atrazine,diuron, chlorotoluron, clethodim, clomazone, and tebuthiuron.

Examples of insecticides and acaricides may include, but are not limitedto, abamectin, pyriproxyfen, acetamiprid, bifenthrin, cyfluthrin,pymetrozine, novaluron, ethiprole, fipronil, and lambda-cyhalothrin.

Examples of fungicides may include, but are not limited to,azoxistrobine, chlorothalonil, epoxiconazole, propiconazole,fenpropidin, folpet, epoxiconazole, tebuconazole, cyprodinil, diazinon,dimethomorph, fipronil, fludioxonil, and captan.

Examples of nematicide may include, but not limited to, fluensulfone.

In some embodiments, the agricultural material is hydrophobicagricultural material.

In some embodiments, the agricultural material is hydrophobicagrochemical.

In some embodiments, the agricultural material is hydrophobic pesticide.

In some embodiments, the particles of the at least one agriculturalmaterial compound is hydrophobic particles.

In some embodiments, the particles are in solution which comprises theagricultural material.

In some embodiments, the particles are solid.

In some embodiments, the particles are liquid.

In some embodiments, the particles are capsules.

In some embodiments, the particles are drops.

In some embodiments, the drops are agricultural material which isdissolved in the solvent.

In some embodiments, the drops are pesticide which is dissolved in thesolvent.

In some embodiments, the particles are agricultural material which isdissolved in the solvent.

In some embodiments, the particles are pesticide which is dissolved inthe solvent.

In some embodiments, the particles are agricultural material which isencapsulated.

In some embodiments, the particles are pesticide which is encapsulated.

In some embodiments, the drops are in solution which comprises theagricultural material.

In some embodiments, the agricultural material is liquid.

In some embodiments, the agricultural material is dissolved in solvent.

In some embodiments, the solvent is non aqueous solvent.

In some embodiments, the solvent is organic solvent.

Solvents may include, but are not limited to, methyloleate (Agnique® ME181), aromatic fluids (Solvesso™), cyclohexanon, N,N-dimethyloctanamide,N,N-dimethyl-decanamide, acetophenone, and octanol.

In one embodiment, the composition further comprises an agriculturallyacceptable carrier. In one embodiment, the composition further comprisesa safener. In one embodiment, the composition further comprises apreservative. In another embodiment, the composition further comprisesat least one additional component/moiety selected from the groupconsisting of surfactants, rheology modifiers, anti-settling agents,antifoam agents, buffers, and liquid diluents. Other ingredients, suchas wetting agents, adhesives, thickeners, binders, colorants such asazo, phthalocyanine or other pigments, or antifreeze agents, may also beadded to the composition in order to increase the stability, density,appearance and ease-of-handling of the composition. In yet anotherembodiment, the agricultural material composition can further compriseadjuvant such as ionic, anionic, nonionic, polymeric/copolymeric, ornon-polymeric/copolymeric surfactants. One exemplary moiety in thisregard can be a penetrant amassment such as a pyrrolidone.

In one embodiment, the composition is an emulsion, a suspension, asuspension concentrate, a capsule suspension, or a suspo-emulsion.

In one embodiment, the composition is an emulsion and the emulsion is anoil in water emulsion. In an oil in water emulsion, the polyelectrolytelayer adsorbed on the surface of the droplets containing at least oneagricultural material compound and stabilizes the droplets as the oilphase of a dispersion, wherein at least one agricultural materialcompound is in the oil phase and is dispersed in a continuous waterphase. By using the presently described block copolymers, the presentdispersions can maintain a high concentration of oil while preservingthe oil in water emulsion system. This permits the emulsion to remainstable, and prevents the inversion of the oil and water phases. In oneembodiment, the oil in water emulsion comprises at least 40, 50, 60, or70% by weight of an oil phrase.

In one embodiment, the composition is an aqueous suspension. In oneembodiment, the aqueous suspension has a concentration of greater than500 g/L of particles of the agricultural material compound. In oneembodiment, the aqueous suspension has a concentration of between 900g/L to 1200 g/L of particles of the agricultural material compound. Inone embodiment, the suspension has a viscosity of less than 750 cPs. Inone embodiment, the suspension contains no thickening agent and has aviscosity of less than 750 cPs. Viscosity is measured using theBrookfield viscometer at spindle 62 and 12 RPM.

In one embodiment, the composition is a suspension concentrate. In oneembodiment, the suspension concentrate further comprises a nonionicsurfactant, an anionic surfactant, and/or an anti-crystallization agent(crystal growth inhibitor).

In one embodiment, the composition is in solid form. In one embodiment,the solid composition is in the form of granules.

The subject invention also provides a method of controlling andpreventing pest comprising applying a pesticidal composition to a locuswhere the pest is to be controlled and prevented, wherein the pesticidalcomposition comprises:

-   -   (i) particles of at least one pesticide compound; and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on surfaces of the        pesticide compound particles.

In one embodiment, the pest is insect. In one embodiment, the pest isfungi. In one embodiment, the pest is nematode. In one embodiment, thepest is weed.

In one embodiment, the locus is a plant, an area adjacent to a plant,soil adapted to support growth of a plant, a root of a plant, foliage ofa plant, and/or a seed adapted to produce a plant.

The present compositions may be applied to healthy or diseased plant. Insome embodiments, the present compositions is applied to various plantsincluding but not limited to crops, seeds, bulbs, propagation material,turf, or ornamental species.

In one embodiment, the locus is a wall, a floor, or a surface of afurniture or fixture. In one embodiment, the locus is a kitchen surfaceor bathroom surface.

In one embodiment, the locus is skin of an animal or surrounding of ananimal. In one embodiment, the locus is a railway or an area surroundinga railway.

The present compositions can be diluted and applied in a customarymanner, for example by watering (drenching), drip irrigation, spraying,and/or atomizing.

The subject invention also provides a method of improving plant growthcomprising applying an agricultural material composition to at least oneof a plant, an area adjacent to a plant, soil adapted to support growthof a plant, a root of a plant, foliage of a plant, and/or a seed adaptedto produce a plant, wherein the composition comprises:

-   -   (i) particles of at least one agricultural material compound;        and    -   (ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the agricultural material compound particles.

In one embodiment, the agricultural material is a plant growthregulator. In one embodiment, the agricultural material is abio-stimulant. In one embodiment, the agricultural material is ahormone.

In one embodiment, the method is effective to increase yield of theplant. In one embodiment, the method is effective to increase growthrate of the plant. In one embodiment, the method is effective toincrease size of the plant.

In some embodiments, the present compositions is applied to variousplants including but not limited to crops, seeds, bulbs, propagationmaterial, or ornamental species.

The present compositions can be diluted and applied in a customarymanner, for example by watering (drenching), drip irrigation, spraying,and/or atomizing.

High-Load Agricultural Material Compositions

In some embodiments of the subject invention, the agricultural materialcomposition is high-load. In some embodiments of the subject invention,the pesticidal composition is high-load.

In one embodiment, the high-load composition is a dispersion. In oneembodiment, the high-load composition is prepared as a stable,accurate-to-dilute, easy-to-dilute concentrated dispersion.

In one embodiment, the concentration of particles in the composition is500, 600, 700, 800, 900, 1000, 1100, or 1200 g/L. In another embodiment,the concentration of particles in the composition is 900-1200 g/L.

In a further embodiment, the density of the composition is about 1.4-1.6kg/L. Dispersible compositions of this density provide enhancedstability of formulations with closed packed particles in thecomposition.

In a further embodiment, the composition comprises about 15-40% byweight of water.

In another embodiment the viscosity of the composition is less than 750cPs. Viscosity measured at spindle 62 and 12 RPM using Brookfieldviscometer.

The present high-load dispersible compositions are advantageous becausethey contain densely packed particles, yet maintain low viscosity andhigh flowability. These compositions can also have a high particleconcentration and very small amounts of water.

The present high-load compositions are also advantageous because theypermit a reduction of package volume of the composition comprising atleast one compound.

In one embodiment, the at least one compound is an agricultural materialcompound. In one embodiment, the agricultural material compound is anagrochemical compound. In one embodiment, the agricultural materialcompound is a pesticide compound. In one embodiment, the agriculturalmaterial compound is a plant growth regulator, a hormone, or abio-stimulant. In one embodiment, the at least one compound is anon-agricultural material compound.

Process of Preparing Compositions

The present invention provides a process of preparing a compositioncomprising mixing particles of at least one compound with an amount of apolyelectrolyte-layer forming block co-polymer, wherein the blockcopolymer comprises (A) an anchoring moiety and (B) at least onestabilizing moiety.

The present invention provides a process of preparing a pesticidalcomposition comprising mixing particles of at least one pesticidecompound with an amount of a polyelectrolyte-layer forming blockco-polymer, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety.

In one embodiment, mixing comprises preparing a dispersion of particlesof the at least one compound and adsorbing the polyelectrolyte-layerforming block copolymer on hydrophobic surfaces of the particles to forma polyelectrolyte layer on the particle interface.

In one embodiment, mixing comprises preparing a dispersion comprisingparticles in up to 20% w/w water of the at least one compound andadsorbing the polyelectrolyte-layer forming block copolymer onhydrophobic surfaces of the particles in the dispersion and forming apolyelectrolyte layer on the particle interface.

In one embodiment, the at least one compound is an agricultural materialcompound. In one embodiment, the agricultural material compound is anagrochemical compound. In one embodiment, the agricultural materialcompound is a pesticide compound. In one embodiment, the agriculturalmaterial compound is a plant growth regulator, a hormone, or abio-stimulant. In another embodiment, the at least one compound is anon-agricultural material compound.

The present invention provides a process of preparing a pesticidalcomposition comprising:

-   -   i) preparing a dispersion comprising particles of at least one        pesticide compound; and    -   ii) adsorbing a polyelectrolyte-layer forming block copolymer,        comprising (A) an anchoring moiety and (B) at least one        stabilizing moiety, on hydrophobic surfaces of the pesticide        compound particles in the dispersion and forming a        polyelectrolyte layer on the particle interface.

In one embodiment, the dispersion is a water dispersion. In oneembodiment, the dispersion has a concentration of agricultural materialparticles of at least 900 g/L.

In one embodiment, the process further comprises a wet milling stepafter the polyelectrolyte layer is formed.

In one embodiment, the amount of the block copolymer is effective toreduce the temperature during milling of the composition compared to thetemperature during milling of the same composition without addition ofthe block co-polymer.

In one embodiment, the amount of block copolymer is effective to reducethe viscosity of the composition during milling of the compositioncompared to the viscosity of the same composition during milling withoutaddition of the block co-polymer.

In another specific embodiment, the temperature during the wet millingprocess is less than 30° C. In one embodiment, the temperature duringmilling is reduced from 40° C.-50° C. to 20° C.-25° C. In oneembodiment, the viscosity during milling is reduced from 1000-2000 cPsto 200-400 cPs. Viscosity is measured using the Brookfield viscometer atspindle 62 and 12 RPM. In yet another specific embodiment, 90% of theparticles have a particle size of 50 μm or greater prior to the wetmilling process and a particle size of 1 μm or less after the wetmilling process.

In one embodiment, the process further comprises a granulation stepafter the polyelectrolyte layer is formed.

In a specific embodiment, the preparation provides an improvedgranulation by reducing the pressure that develops during granulation.In one embodiment, the amount of block copolymer is effective to reducethe pressure during granulation of the composition compared to thepressure during granulation of the same composition without addition ofthe block co-polymer.

Improving the Granulation Process of Compositions

The subject invention provides a method of reducing pressure duringgranulation of a composition comprising at least one compound by addingan amount of a polyelectrolyte-layer forming block copolymer to thecomposition, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety, and wherein the amountof block copolymer is effective to reduce the pressure duringgranulation of the composition compared to the pressure duringgranulation of the same composition without addition of the blockco-polymer.

In one embodiment, the at least one compound is an agricultural materialcompound. In one embodiment, the agricultural material compound is anagrochemical compound. In one embodiment, the agricultural materialcompound is a pesticide compound. In one embodiment, the agriculturalmaterial compound is a plant growth regulator, a hormone, or abio-stimulant. In another embodiment, the at least one compound is anon-agricultural material compound.

Granulation is a process used for preparing water dispersible granulesformulations. In the process of granulation, after milling the activeingredient(s) with solid additives, some amount of water (up to 30% w/w)is added. The present block copolymer is added together with this water.Then the powder is introduced to the granulator. The granulator, made ofwings rotating at a certain speed (which is determined by the user),pushes the powder through a screen with small holes. In hard cases thepowder creates a large pressure that resists this transfer through thescreen.

The polyelectrolyte layer formed on the particles using the blockcopolymer improves granulation by remarkably reducing the pressure thatdevelops during the granulation process.

Improving the Wet Milling Process of Compositions

The subject invention provides a method of reducing viscosity of acomposition comprising at least one compound during milling of thecomposition by adding an amount of a polyelectrolyte-layer forming blockcopolymer to the composition, wherein the block copolymer comprises (A)an anchoring moiety and (B) at least one stabilizing moiety, and whereinthe amount of block copolymer is effective to reduce the viscosity ofthe composition during milling of the composition compared to theviscosity of the same composition during milling without addition of theblock co-polymer.

The subject invention provides a method of reducing temperature duringmilling of a composition comprising at least one compound by adding anamount of a polyelectrolyte-layer forming block copolymer to thecomposition, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety, and wherein the amountof block copolymer is effective to reduce the temperature during millingof the composition compared to the temperature during milling of thesame composition without addition of the block co-polymer.

In one embodiment, the at least one compound is an agricultural materialcompound. In one embodiment, the agricultural material compound is anagrochemical compound. In one embodiment, the agricultural materialcompound is a pesticide compound. In one embodiment, the agriculturalmaterial compound is a plant growth regulator, a hormone, or abio-stimulant. In another embodiment, the at least one compound is anon-agricultural material compound.

Wet milling is a process used for preparing suspension concentrateformulations. The polyelectrolyte layer formed by the block copolymersignificantly lowers/reduces interactions between the particles therebyreducing viscosity and allowing the suspension to be loaded with a highconcentration of particles without increasing the temperature of thesystem. In some embodiments, the temperature during milling a 1000 g/Lsuspension of the present compositions is less than 30° C. In oneembodiment, the temperature during milling is reduced from 40° C.-50° C.to 20° C.-25° C. In one embodiment, the viscosity during milling isreduced from 1000-2000 cPS to 200-400 cPs. Viscosity is measured usingthe Brookfield viscometer at spindle 62 and 12 RPM. In some embodiments,the particle size of 90% of the particle decreases from 50 μm to 1 μm asa result of the wet milling process.

Accordingly, the present subject matter permits greater density of theformulations and an efficient, low temperature wet milling process.

Improving Stability of Compositions in High Salt Environment

The polyelectrolyte-layer forming block copolymers of the subjectinvention can function as an adjuvant, and more specifically as a stericdispersant under various conditions in a highly ionic solution. Use ofthe block copolymers of the subject invention stabilizes, e.g. byprevents or delays settlement of, the particles of compounds in highsalt environment.

In one embodiment, the compound is an agricultural material compound. Inone embodiment, the agricultural material compound is an agrochemicalcompound. In one embodiment, the agricultural material compound is apesticide compound. In one embodiment, the agricultural materialcompound is a plant growth regulator, a hormone, or a bio-stimulant. Inanother embodiment, the compound is a non-agricultural materialcompound.

Non-Agricultural Material Compositions and Uses Thereof

The subject invention provides a non-agricultural material compositioncomprising:

-   -   (i) particles of at least one non-agricultural material        compound, and    -   (ii) a dispersing system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the block co-polymer is adsorbed on hydrophobic surfaces        of the non-agricultural material particles.

The subject application provides a colorant system compositioncomprising:

-   -   a) a colorant component; and    -   b) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the colorant system composition is produced as a        dispersion.

In one embodiment, the colorant component may comprise at least onecolorant particle and the block co-polymer is adsorbed on a hydrophobicsurface of the colorant particle.

In one embodiment, the dispersant system further comprises a seconddispersant. In one embodiment, the second dispersant is at least one ofa polymeric dispersant, polycarboxylate, sodium polyacrylate, glycol,diethylene glycol, glycerine, C₆₋₁₈ alcohol ethoxylate and its sulfateor phosphate, sorbitan monoleate, tristyryl phenol ethoxylate,nopol-containing surfactant or eicosa(propoxy)deca(ethoxy)diethylamine.

In one embodiment, the colorant composition has a VOC (Volatile OrganicContent) of less than about 100 g/L.

In one embodiment, the colorant composition is compatible with bothlatex-based coatings and alkyd-based coatings.

The subject invention provides a method of tinting an alkyd-based basecoating or a latex-based base coating comprising contacting thealkyd-based base coating or the latex-based base coating with a colorantsystem composition, wherein the colorant system composition comprises:

-   -   i) a colorant component; and    -   ii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety,    -   wherein the colorant system composition is prepared as a        dispersion.

The subject invention also provides an aqueousnon-agricultural-application-based composition comprising at least:

-   -   i) one non-agricultural material compound;    -   ii) water; and    -   iii) a dispersant system comprising a polyelectrolyte-layer        forming block copolymer, wherein the block copolymer        comprises (A) an anchoring moiety and (B) at least one        stabilizing moiety.

In one embodiment, the aqueous non-agricultural-application-basedcomposition is an emulsion comprising an effective amount of thedispersant system and a film forming polymer latex.

In one embodiment, the aqueous non-agricultural-application-basedcomposition further comprises one or more of a pigment, a filler, or anextender.

In one embodiment, the aqueous non-agricultural-application-basedcomposition is an emulsion selected from the group consisting of a latexpaint, a latex coating, a cosmetic, a detergent/cleanser, a stimulationfluid and an oilfield drilling fluid. In one embodiment, the emulsion isa latex paint.

In one embodiment, the aqueous non-agricultural-application-basedcomposition further comprises at least one additive selected from thegroup consisting of surfactants, rheology modifiers, defoamers,thickeners, colorants, waxes, perfumes and co-solvents.

The subject invention provides a method of preparing a coatingcomposition comprising contacting a film forming polymer latex with adispersant system comprising a polyelectrolyte-layer forming blockcopolymer, wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety.

The one embodiment, the method further comprises contacting the filmforming polymer latex with water.

The subject invention provides a method of preparing a colorant systemcomposition comprising contacting a colorant component with a dispersantsystem comprising a polyelectrolyte-layer forming block copolymerwherein the block copolymer comprises (A) an anchoring moiety and (B) atleast one stabilizing moiety, and wherein the resulting colorant systemcomposition is a dispersion.

The subject invention also provides a polyelectrolyte-layer formingblock copolymer for use as an additive in oil cement grout. In someembodiments, the polyelectrolyte-layer forming block copolymer is usedas a suspending agent in the oil cement grout.

In one embodiment, the polyelectrolyte-layer forming block copolymer ofthe invention, in combination with the solid particles present in thecement, provides the dispersing effect during the cementing.

The subject invention also provides an oil cement grout comprising solidparticles and a polyelectrolyte-layer forming block copolymer whereinthe block copolymer comprises (A) an anchoring moiety and (B) at leastone stabilizing moiety.

The subject invention also provides use of a polyelectrolyte-layerforming block copolymer for keeping solid particles in suspension in anoil cement grout, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety.

Polyelectrolyte-Layer Forming Block Copolymers and Method of Preparation

The polyelectrolyte-layer forming block copolymer of the subjectinvention has one of the structures A, B and C, shown in FIGS. 7, 8 and9, respectively.

A) a di-block copolymer is a linear polymer/copolymer and consists of ablock of hydrophobic moiety (anchoring moiety) and a block of ahydrophilic charged moiety (stabilizing moiety). (see FIG. 7)

B) a tri-block copolymer is a linear polymer/copolymer and consists of ahydrophobic moiety and two blocks of hydrophilic charged moiety. (seeFIG. 8)

C) a comb-graft polymer/copolymer consists of a hydrophobic moiety andmultiple blocks of a hydrophilic charged moiety, for example 4 blocks ofhydrophilic charged moiety as represented in FIG. 9. This can bereferred to simply as a grafted copolymer.

The adsorption of the polyelectrolyte-layer forming block copolymerdescribed in the subject invention may be measured by a number oftechniques.

For example, the polyelectrolyte-layer forming block copolymer of thesubject invention may be added to a dispersion of particles in anaqueous medium. After time, the serum may be obtained by centrifuging orfiltration of the slurry. The resultant serum could be injected into asize exclusion chromatography device running the relevant method toseparate polymer from the matrix and its concentration determined usinga calibration curve obtained by injecting polymer samples of knownconcentration. Alternatively the centrifuged particles could be washedand their zeta potential measured using equipment known to those skilledin the art. The adsorption of the polyelectrolyte-layer forming blockcopolymer will result in a net increase of negative charge on theparticle surface which corresponds to the formation of a polyelectrolytebrush layer from the adsorbed polymer.

In one embodiment of the subject invention, the anchoring moiety is ahydrophobic block copolymer. In one embodiment, at least 90% of theanchoring moiety comprises hydrophobic monomers. In some cases, a smallamount of hydrophilic monomers (i.e., less than 10% by monomer number)may be introduced to the block.

In one embodiment, the hydrophobic monomers is selected from the groupconsisting of acrylate derivatives, methacrylate derivatives, styrenederivatives, and any combination thereof. An alkyl acrylate monomer,such as a methyl, ethyl, or butyl acrylate, is one exemplary embodimentin this regard.

In one embodiment, the hydrophobic monomer is selected from a groupconsisting of methylacrylate, ethylacrylate, n-propylacrylate,n-butylacrylate, 2-ethyl-hexyl acrylate, methylmethacrylate,ethylmethacrylate, n-propylmethacrylate, n-butylmethacrylate and2-ethyl-hexyl methacrylate. In one embodiment, the hydrophobic monomeris ethyl acrylate.

In one embodiment, the at least one stabilizing moiety is a hydrophilicblock copolymer. In one embodiment, the at least one stabilizing moietycomprises charged monomers. In one embodiment, at least 60% by weight ofthe stabilizing moiety is charged monomers. In one embodiment, at least70% by weight of the stabilizing moiety is charged monomers. In oneembodiment, at least 80% by weight of the stabilizing moiety is chargedmonomers. In one embodiment, at least 90% by weight of the stabilizingmoiety is charged monomers. In one embodiment, 100% by weight of thestabilizing moiety is charged monomers.

In one specific embodiment, the weight percentage of the chargedmonomers in the stabilizing block is 77% of the weight of thestabilizing block. In another specific embodiment, the weight percentageof the charged monomers in the stabilizing block is 88% of the weight ofthe stabilizing block. In another specific embodiment, the weightpercentage of the charged monomers in the stabilizing block is 68% ofthe weight of the stabilizing block. In another specific embodiment, theweight percentage of the charged monomers in the stabilizing block is83% of the weight of the stabilizing block.

In another embodiment, the weight percentage of the charged monomers ofthe stabilizing polymer is at least 35% of the total weight of the blockcopolymer. In another embodiment, the weight percentage of the chargedmonomers of the stabilizing polymer is 58% of the total weight of theblock copolymer.

In one embodiment, the charged monomers are zwitterionic monomers. Inone embodiment, the charged monomers are anionic monomers. In oneembodiment, at least 60% of the monomers in the stabilizing block areanionic monomers. In one embodiment, the anionic monomer has a sulfonategroup. In one embodiment, the anionic monomer is2-acrylamido-2-methylpropane sulphonate (AMPS).

In one embodiment, less than 40% of the monomers in the stabilizingblock is neutral hydrophilic monomers. In one embodiment, the neutralhydrophilic monomer is selected from a group consisting ofN-vinylpyrrolidone, ethylene oxide, glycoside acrylate, and acrylamide.

In another embodiment, the weight percentage of the stabilizing block is65-90% of the total weight of the block copolymer.

In one embodiment, the concentration of the block copolymer in thecomposition is about 0.1%, 0.5%, 1.0%, 1.5%, or 2.0% w/w. In oneembodiment, the concentration of the block copolymer in the compositionis 0.2-3% w/w.

In one embodiment, the block copolymer comprises up to 150 monomers. Inone embodiment, the block copolymer comprises 85 monomers. In oneembodiment, the block copolymer comprises 63 monomers.

In another embodiment, the weight of the block copolymer is up to about31000 g/mol. In one embodiment, the weight of the block copolymer isabout 17000 g/mol. In another embodiment, the weight of the blockcopolymer is about 12000 g/mol. In one embodiment, the weight of theblock copolymer is 8,000 to 50,000 g/mol. In one embodiment, the weightof the block copolymer is 10,000 to 25,000 g/mol.

In one embodiment, the weight of the stabilizing block is 5,000 to100,000 g/mol. In one embodiment, the weight of the stabilizing block is6,000 to 50,000 g/mol. In one embodiment, the weight of the stabilizingblock is 7,000 to 30,000 g/mol.

In one embodiment, the weight of the anchoring moiety is 500 to 5,000g/mol. In one embodiment, the weight of the anchoring moiety is 1,000 to4,000 g/mol.

In one embodiment, the anchoring moiety comprises alkyl acrylatemonomers, preferably ethyl acrylate monomers, and the weight of theanchoring moiety is 1,000 to 4,000 g/mol. In one embodiment, theanchoring moiety comprises alkyl acrylate monomers, preferably ethylacrylate monomers, and the weight of the anchoring moiety is 1,500 to3,500 g/mol. In one embodiment, the anchoring moiety comprises alkylacrylate monomers, preferably ethyl acrylate monomers, and the weight ofthe anchoring moiety is 1,500 to 3,000 g/mol.

In one embodiment, the molar ratio of the anchoring moiety to thestabilizing moiety is 1:2-4.

In one embodiment, the weight ratio between the anchoring moiety and thestabilizing moiety ([anchoring moiety]:[stabilizing moiety]) is lowerthan 0.6, lower than or equal to 0.5, lower than or equal to 0.4, lowerthan or equal to 0.3, or lower than or equal to 0.2. In one embodiment,the weight ratio between the anchoring moiety and the stabilizing moiety([anchoring moiety]:[stabilizing moiety]) is between 0.01 and 0.6. Inone embodiment, the weight ratio between the anchoring moiety and thestabilizing moiety ([anchoring moiety]:[stabilizing moiety]) is between0.1 and 0.3.

The block copolymer of the subject invention can be synthesized by raftand polymer/copolymerization.

According to any one of the invention embodiments, thepolyelectrolyte-layer forming block copolymer of the inventioncomprises:

-   -   (A) an anchoring moiety obtained by polymerization of at least        one monomer selected from the group consisting of        methylacrylate, ethylacrylate, n-propylacrylate,        n-butylacrylate, 2-ethyl-hexyl acrylate, methylmethacrylate,        ethylmethacrylate, n-propylmethacrylate, n-butylmethacrylate and        2-ethyl-hexyl methacrylate, especially from methylacrylate,        ethylacrylate, or butyl acrylate; said anchoring moiety        comprising at least 90 wt % of units derived from said monomers,        and said anchoring moiety having a molecular weight ranging from        1,000 to 4,000 g/mol, for example from 1,500 to 3,500 g/mol, for        example from 1,500 to 3,000 g/mol;    -   (B) a stabilizing moiety obtained by polymerization of at least        one anionic monomer, in particular one anionic monomer having a        sulphonate group, preferably 2-acrylamido-2-methylpropane        sulphonate; said stabilizing moiety comprising at least 60 wt %        of units derived from said anionic monomer, and said stabilizing        moiety having a molecular weight ranging from 6,000 to 50,000        g/mol, for example from 7,000 to 30,000 g/mol;

with the weight ratio between the anchoring block and the stabilizingblock ranging between 0.1 and 0.3, and

-   -   with said copolymer having an overall molecular weight        preferably ranging from 8,000 to 50,000 g/mol, for instance from        10,000 to 25,000 g/mol.

There are several methods for making a polyelectrolyte-layer formingblock copolymer of the invention. Some methods for making suchcopolymers are provided below.

In the context of the present invention, living or controlledpolymerization as defined by Quirk and Lee (Polymer International 27,359 (1992)) can be used. This particular method makes it possible toprepare polymers with a narrow dispersity and in which the length andthe composition of the blocks are controlled by the stoichiometry andthe degree of conversion. In the context of this type of polymerization,there are more particularly recommended copolymers which can be obtainedby any so-called living or controlled polymerization method such as, forexample:

-   -   free-radical polymerization controlled by xanthates according to        the teaching of PCT International Application Publication No. WO        98/58974 and U.S. Pat. No. 6,153,705,    -   free-radical polymerization controlled by dithioesters according        to the teaching of PCT International Application Publication No.        WO 98/01478,    -   free-radical polymerization controlled by dithioesters according        to the teaching of PCT International Application Publication No.        WO 99/35178,    -   free-radical polymerization controlled by dithiocarbamates        according to the teaching of PCT International Application        Publication No. WO 99/35177,    -   free-polymerization using nitroxide precursors according to the        teaching of PCT International Application Publication No. WO        99/03894,    -   free-radical polymerization controlled by dithiocarbamates        according to the teaching of PCT International Application        Publication No. WO 99/31144,    -   free-radical polymerization controlled by dithiocarbazates        according to the teaching of PCT International Application        Publication No. WO 02/26836,    -   free-radical polymerization controlled by halogenated Xanthates        according to the teaching of PCT International Application        Publication No. WO 00/75207 and U.S. application Ser. No.        09/980,387,    -   free-radical polymerization controlled by dithiophosphoroesters        according to the teaching of PCT International Application        Publication No. WO 02/10223,    -   free-radical polymerization controlled by a transfer agent in        the presence of a disulphur compound according to the teaching        of PCT International Application Publication No. WO 02/22688,    -   atom transfer radical polymerization (ATRP) according to the        teaching of PCT International Application Publication No. WO        96/30421,    -   free-radical polymerization controlled by iniferters according        to the teaching of Otu et al., “Role of Initiator-Transfer        Agent-Terminator (Iniferter) in Radical Polymerizations: Polymer        Design by Organic Disulfides as Iniferters”, Makromol. Chem.        Rapid. Commun., 3, 127 (1982),    -   free-radical polymerization controlled by degenerative transfer        of iodine according to the teaching of Tatemoto et al., Jap. 50,        127, 991 (1975), Daikin Kogyo Co Ltd Japan, and Matyjaszewski et        al., “Controlled Radical Polymerizations: The Use of Alkyl        Iodides in Degenerative Transfer”, Macromolecules, 28, 2093        (1995),    -   group transfer polymerization according to the teaching of        Webster O. W., “Group Transfer Polymerization”, p. 580-588, in        the “Encyclopedia of Polymer Science and Engineering”, Vol. 7,        edited by H. F. Mark, N. M. Bikales, C. G. Overberger and G.        Menges, Wiley Interscience, New York, 1987,    -   radical polymerization controlled by tetraphenylethane        derivatives (D. Braun et al., “Initiation of Free Radical        Polymerization by Thermal Cleavage of Carbon-Carbon Bonds”,        Macromol. Symp., 111, 63 (1996)),    -   radical polymerization controlled by organocobalt complexes        (Wayland et al., “Living Radical Polymerization of Acrylates by        Organocobalt Porphyrin Complexes”, J. Am. Chem. Soc., 116, 7973        (1994)).

The entire content of each of the documents cited above as exemplaryliving or controlled polymerization processes are incorporated byreference herein.

Preferred processes are sequenced living free-radical polymerizationprocesses involving the use of a transfer agent.

Preferred transfer agents are agents comprising a group of formula—S—C(S)—Y—, —S—C(S)—S—, or —S—P(S)—Y—, or —S—P(S)—S—, wherein Y is anatom different from sulfur, such as an oxygen atom, a nitrogen atom, anda carbon atom. They include dithioester groups, thioether-thione groups,dithiocarbamate groups, dithiphosphoroesters, dithiocarbazates, andxanthate groups. Examples of groups comprised in preferred transferagents include groups of formula —S—C(S)—NR—NR′2, —S—C(S)—NR—N═CR′2,—S—C(S)—O—R, —S—C(S)—CR′CR′2, and —S—C(S)—X, wherein R and R′ are oridentical or different hydrogen atoms, or organic groups such ashydrocarbyl groups, optionally substituted, optionally comprisingheteroatoms, and X is an halogen atom. A preferred polymerizationprocess is a living radical polymerization using xanthates.

Copolymers obtained by a living or controlled free-radicalpolymerization process may comprise at least one transfer agent group atan end of the polymer chain. In particular embodiment such a group isremoved or deactivated.

A living or controlled radical polymerization process used to make theblock copolymers comprises the steps of:

-   -   a) reacting a mono-alpha-ethylenically-unsaturated monomer, at        least a free radicals source compound, and a transfer agent, to        obtain a first block, the transfer agent being bounded to said        first block,    -   b1) reacting the first block, another        mono-alpha-ethylenically-unsaturated monomer, and, optionally,        at least a radical source compound, to obtain a di-block        copolymer,    -   b2) optionally, repeating n times (n being equal to or greater        than 0) step b1) to obtain a (n-2)-block copolymer, and then    -   c) optionally, reacting the transfer agent with means to render        it inactive.

For example, a “living” or “controlled” radical polymerization processused to make the di-block copolymers comprises the steps of:

-   -   a) reacting a mono-alpha-ethylenically-unsaturated monomer, at        least a free radicals source compound, and a transfer agent, to        obtain a first block, the transfer agent being bounded to said        first block,    -   b) reacting the first block, another        mono-alpha-ethylenically-unsaturated monomer, and, optionally,        at least a radical source compound, to obtain a di-block        copolymer, and then    -   c) optionally, reacting the transfer agent with means to render        it inactive.

During step a), a first block of the polymer is synthesized. During stepb), b1), or b2), another block of the polymer is synthesized.

Examples of transfer agents are transfer agents of the following formula(I):

wherein:

-   -   R represents an R2O—, R2R′2N— or R3— group, R2 and R′2, which        are identical or different, representing (i) an alkyl, acyl,        aryl, alkene or alkyne group or (ii) an optionally aromatic,        saturated or unsaturated carbonaceous ring or (iii) a saturated        or unsaturated heterocycle, it being possible for these groups        and rings (i), (ii) and (iii) to be substituted, R3 representing        H, Cl, an alkyl, aryl, alkene or alkyne group, an optionally        substituted, saturated or unsaturated (hetero)cycle, an        alkylthio, alkoxycarbonyl, aryloxycarbonyl, carboxyl, acyloxy,        carbamoyl, cyano, dialkyl- or diarylphosphonato, or dialkyl- or        diarylphosphinato group, or a polymer chain,    -   R1 represents (i) an optionally substituted alkyl, acyl, aryl,        alkene or alkyne group or (ii) a carbonaceous ring which is        saturated or unsaturated and which is optionally substituted or        aromatic or (iii) an optionally substituted, saturated or        unsaturated heterocycle or a polymer chain, and

The R1, R2, R′2 and R3 groups can be substituted by substituted phenylor alkyl groups, substituted aromatic groups or the following groups:oxo, alkoxycarbonyl or aryloxycarbonyl (—COOR), carboxyl (—COOH),acyloxy (—O2CR), carbamoyl (—CONR2), cyano (—CN), alkylcarbonyl,alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, isocyanato,phthalimido, maleimido, succinimido, amidino, guanidino, hydroxyl (—OH),amino (—NR2), halogen, allyl, epoxy, alkoxy (—OR), S-alkyl, S-aryl orsilyl, groups exhibiting a hydrophilic or ionic nature, such as alkalinesalts of carboxylic acids or alkaline salts of sulphonic acid,poly(alkylene oxide) (PEO, PPO) chains, or cationic substituents(quaternary ammonium salts), R representing an alkyl or aryl group.

Preferably, the transfer agent of formula (I) is a dithiocarbonatechosen from the compounds of following formulae (IA), (IB) and (IC):

wherein:

-   -   R2 and R2′ represent (i) an alkyl, acyl, aryl, alkene or alkyne        group or (ii) an optionally aromatic, saturated or unsaturated        carbonaceous ring or (iii) a saturated or unsaturated        heterocycle, it being possible for these groups and rings        (i), (ii) and (iii) to be substituted,    -   R1 and R1′ represent (i) an optionally substituted alkyl, acyl,        aryl, alkene or alkyne group or (ii) a carbonaceous ring which        is saturated or unsaturated and which is optionally substituted        or aromatic or (iii) an optionally substituted, saturated or        unsaturated heterocycle or a polymer chain, and    -   p is between 2 and 10.

Other examples of transfer agents are transfer agents of the followingformulae (II) and (III):

wherein

-   -   R1 is an organic group, for example a group R1 as defined above        for transfer agents of formulae (I), (IA), (IB), and (IC),    -   R2, R3, R4, R7, and R8 which are identical or different are        hydrogen atoms or organic groups, optionally forming rings.        Examples of R2, R3, R4, R7, and R8 organic groups include        hydrocarbyls, substituted hydrocabyls, heteroatom-containing        hydrocarbyls, and substituted heteroatom-containing        hydrocarbyls.

The mono-alpha-ethylenically-unsaturated monomers and their proportionsare chosen in order to obtain the desire properties for the block(s).According to this process, if all the successive polymerizations arecarried out in the same reactor, it is generally preferable for all themonomers used during one stage to have been consumed before thepolymerization of the following stage begins, therefore before the newmonomers are introduced. However, it may happen that monomers of thepreceding stage are still present in the reactor during thepolymerization of the following block. In this case, these monomersgenerally do not represent more than 5 mol % of all the monomers.

The polymerization can be carried out in an aqueous and/or organicsolvent medium. The polymerization can also be carried out in asubstantially neat melted form (bulk polymerization), or according to alatex type process in an aqueous medium.

Each embodiment disclosed herein is contemplated as being applicable toeach of the other disclosed embodiments. Thus, all combinations of thevarious elements described herein are within the scope of the invention.In addition, the elements recited in composition embodiments can be usedin the method and use embodiments described herein and vice versa.

EXAMPLES

Examples are provided below to facilitate a more complete understandingof the present subject matter. The following examples illustrate theexemplary modes of making and practicing the present subject matter.However, the scope of the present subject matter is not limited tospecific embodiments disclosed in these Examples, which are for purposesof illustration only. Other embodiments will be apparent to one skilledin the art from consideration of the specification and examples. It isintended that the specification, including the examples, is consideredexemplary only without limiting the scope and spirit of the presentsubject matter.

Example 1 Polyelectrolyte-Layer Forming Block Copolymer A (PolyAgro A)Formulation

The formulation of an exemplary block copolymer according to the presentsubject matter, labeled herein as PolyAgro A, is represented below inTable 1:

TABLE 1 Total STAB ANCHOR AMPS EA AMPS EA Mnth Mnth Mnth Dpn Dpn (mol %)(mol %) (wt %) (wt %) (g/mol) (g/mol) (g/mol) STAB ANCHOR 77 23 88 1217000 15000 2000 65 20

PolyAgro A is a di-block copolymer, with a total weight of 17000 g/mol,composed of a hydrophobic block (Anchor block—ANCHOR) and a hydrophilicblock (Stabilizing block—STAB). The stabilizing, hydrophilic, block ismade of sodium 2-Acryloylamino-2-methylpropane-1-sulfonate (AMPS)monomers, which are 77% of the overall monomers in the polymer. Theother 23% of the monomers belongs to the anchor, hydrophobic, blockwhich is made of ethyl acrylate monomers. The total amount of monomersin the polymer (degree of polymerization, DPn) is 85 monomers.

This polymer may be obtained according to the following procedure.

a) Macro CTA

Into a 2 L double jacketed reactor equipped with mechanical agitator andreflux condenser was added 11.26 g ofO-ethyl-S-(1-methoxycarbonylethyl)xanthate (CH3CH(CO2CH3))S(C═S)OEt),264.08 g of Ethanol, and 356.32 g of De-ionized water and 1400 g ofAMPS(Na) solution (50% active) and 1.52 g of4,4′-Azobis(4-cyanopentanoic acid). The reactor contents were heated to70° C. under agitation and nitrogen. The reaction mixture was aged at70° C. for a further hour whereupon it was cooled to ambient temperatureand discharged. The measured solids content was 37.6% (115° C., 60mins). GPC Mals: Mn=16300 Mw=2600 IP=1.6.

b) Chain Extension

Into a 5 L double jacketed reactor equipped with mechanical agitator andreflux condenser was added 2127 g of macro CTA solution (see a) and 330g of de-ionized water. The reactor contents were heated to 70° C. underagitation and a nitrogen stream. Once 70° C. was reached, 106.67 g ofethyl acrylate (EA) was added over 2 H 00 and a 37.37 g of a solution of10 wt % of 4,4′-Azobis(4-cyanopentanoic acid) was concomitantly addedover 2 h 30. After the end of the introduction of the initiatorsolution, the reaction solution was further aged for one hour.Thereafter a shot of 44.85 g of a 10 wt % solution of4,4′-Azobis(4-cyanopentanoic acid) was added and the mixture aged at 70°C. for a further hour whereupon it was cooled to ambient temperature anddischarged. The measured solids content was 40.0% (115° C., 60 mins).

Ethanol was removed from the polymer solution using a rotary evaporator.Water was back added to achieve a polymer solution with a final solidscontent of 40.4%.

2600 g of polymer solution was placed in a 5 L double jacketed reactorequipped with mechanical agitator and reflux condenser. The pH of thesolution was increased to 8.5 using a 50% solution of NaOH. The mixturewas heated to 70° C. with stirring whereupon 48.4 of a 30% solution ofhydrogen peroxide was added in 1 hour. At the end of the additions, thesolution was aged for a further 3 h 00 whereupon it was cooled anddischarged.

The residuals monomers were measure by HPLC and GC (AMPS=22 ppm, EA=2ppm).

The measured solids content was 37.5%. The polymer is used in theformulations according to the below examples from a ready aqua polymersolution at concentration of about 30% w/w.

Example 2 Effect On the Milling Process

This example provides a comparison between milling suspensionconcentrate formulations with and without PolyAgro A. These formulationsare both considered high load formulations and differ only by thedispersants used.

In Formulation 1, a conventional polymeric dispersant was used (Atlox™4913—a non-ionic grafted copolymer). In Formulation 2, the dispersantsystem used contains the present di-block copolymer PolyAgro A2 (note:PolyAgro A2 is a water solution with 30% w/w of the PolyAgro Apolymer/copolymer of Example 1 as shown above in Table 1). The millingprocess of the two samples is identical.

The active ingredient and the dispersant are introduced into the mixturewithin three steps, between the steps the mixture is being milled andthe viscosity and size distribution of the particles in the mixture ismeasured, as described in more detail below.

Formulation 1 comprising Folpet 1000 g/L as a suspension was prepared byusing Atlox™ 4913 as dispersant. Formulation 2 comprising Folpet 1000g/L as a suspension was prepared by using PolyAgro A2 as dispersant.

The active ingredient is added in three steps and so are the dispersantsand the wetting agent (Emcol 4500, Sodium dioctyl sulfosuccinate). Abouthalf of the Folpet is added immediately, then it is milled, anotheramount of Folpet is added (˜32%) and milled again. On the last step therest of Folpet is added and milled.

Formulation 1 and Formulation 2 are summarized in Table 2A and 2B below.

TABLE 2 Formulation 2-with PolyAgro A2 Formulation 1-without PolyAgro A2% Total Step 1 Step 2 Step 3 % Total Step 1 Step 2 Step 3 IngredientSupplier w/w (g/L) (g) (g) (g) w/w (g/L) (g) (g) (g) Folpet 98% AdamaActive 71.00 1054.4 500.0 335.0 219.4 71.00 1054.4 500.0 335.0 219.4tech Makhteshim ingredient Atlox ™ Croda polymethyl 1.45 21.5 9.7 6.95.0 2.73 40.5 18.2 13.0 9.3 4913 methacrylate- polyethylene glycol graftcopolymer PolyAgro A2 Solvay AMPS-EA 1.28 19.0 8.6 6.1 4.4 0.00 0.0 0.00.0 0.0 diblock copolymer (2 Da-15 Da), ~30% aqua solution LankropolAkzoNobel Sodium 0.65 9.7 4.4 3.1 2.2 0.77 11.4 5.1 3.7 2.6 KO2 dioctylsulpho- succinate Water Solvent 21.52 319.6 319.6 21.40 317.8 317.8Other 4.1 60.8 60.8 4.1 60.8 60.8 3.1 2.2 ingredients Sum 100.00 1485100.00 1485

Before and after each step the viscosity and particle size is measuredand the temperature during milling is constantly followed. (see FIGS. 1and 2)

Turning to FIG. 1, this graph presents the change in the viscositybetween the steps for Formulation 1—without PolyAgro A2, and forFormulation 2—with PolyAgro A2. After each addition of active ingredientpowder, in every step, the viscosity increases, while after milling ineach step the viscosity reduces. In the case of the formulation withoutthe PolyAgro A2, the viscosity rise is dramatically steeper than in thecase of the formulation with the PolyAgro A2.

Looking at FIG. 2, this graph presents the change in the particle sidedistribution (PSD) during the process (d90 is a value which 90%, byvolume, of the particles has smaller diameter). It shows that thePolyAgro A2 polymer doesn't damage the efficacy of the milling, and thatin both cases the reduction in d90 is similar.

Example 3 Stabilization Test In High Salt Condition

High concentration salt solutions with equal amounts of differentdispersants were prepared. A dried-milled active ingredient wasdispersed in the solution and left for a certain period of time. Thesedimentation was then compared between the different solutions. Thecomposition, i.e., type of salt, concentrations, dispersants, activeingredient, is specified for each set of measurements in Table 3 below.

TABLE 3 Pymetrozine Folpet tech. Folpet tech. Active tech. milled.Folpan tech. milled. milled. ingredient 10% w/w milled. 9% w/w 4.5% w/w4.5% w/w salt ammonium Sodium ammonium Calcium sulfate chloride sulfatechlorid 10% w/w 10% w/w 10.5% w/w 10.5% w/w Dispersing 1% 1% 1% 1% agentResults After 24 hrs After After 1 hr After 5 hrs taken overnight

Further analysis of the performance of formulations containing thePolyAgro A2 dispersant vs. other known dispersants can be seen in thepresent figures. FIGS. 3A and 3B provides a comparison of performancesof different known dispersants and of the PolyAgro A2 dispersant in highsalt solutions. Here an equal amount of active ingredient powder(Pymetrozine) was dispersed in different dispersant solutions (1% w/w)with high salt concentration (ammonium sulfate 10% w/w). After 24 hrsthe only powder which remained dispersed is the one dispersed in thePolyAgro A2 polymer dispersant solution. In the rest of the tubes thepowder settled to the bottom.

Similarly, FIG. 4 provides a further comparison of performances ofdifferent known dispersants and of the PolyAgro A2 dispersant in highsalt solutions. Here an equal amount of active ingredient powder(Folpet) was dispersed in different dispersant solutions (1% w/w) withhigh salt concentration (Sodium chloride 10% w/w). After sittingovernight the only powder remaining dispersed is the one dispersed inthe PolyAgro A2 polymer dispersant solution (3 different batches). Inthe rest of the tubes the powder settled to the bottom.

Likewise, FIGS. 5A and 5B provides another comparison of performances ofdifferent known dispersants and of the PolyAgro A2 dispersant in highsalt solutions. Here an equal amount of active ingredient powder(Folpet) was dispersed in different dispersant solutions (1% w/w) withhigh salt concentration (FIG. 5A—ammonium sulfate 10% w/w; FIG.5B—Calcium chloride 10.5% w/w). After some time (1 hr for FIG. 5A, 5 hrsfor FIG. 5B) the only powder remaining dispersed is the one dispersed inthe PolyAgro A2 polymer dispersant solution (3 different batches). Inthe rest of the tubes the powder settled to the bottom.

Example 4 Effect on Granulation Process

Below in Table 4 is a comparison of three different compositions withand without the polyelectrolyte-layer forming block copolymers of thesubject invention.

TABLE 4 Ingredients Supplier Sample 1 Sample 2 Sample 3 Pymetrozine29.7% 29.7% 29.7% tech. (98.2%) Dinotefuran 11.9% 11.9% 11.9% tech.(98.0%) Lactose Starch 25.3% 25.3% 25.3% Ufoxane 3A Borregaard Sodiumlignosulfonate  7.0%  7.0% 7.0% LignoTech Agrilan ® 789 AkzoNobelhydrophobically modified  5.0%  5.0%  5.0% Agrochemicals polyacrylateSupragil ® WP Solvay Sodium Isopropyl  5.0%  5.0%  5.0% NaphthaleneSulfonate Silfoam ® Wacker Chemie Silicone-based powder  2.0%  2.0% 2.0% SP-150 AG antifoam agent Atlox ™ 4913 Croda polymethylmethacrylate-  0.7% polyethylene glycol graft copolymer Ammonium 12.0%12.0% 12.0% sulfate Soprophor Solvay Tristyrylphenol   2% 3D33Ethoxylate Phosphate Ester) Break-THRU S Evonik Polyether Modified   2%240 Trisiloxane PolyAgro A2 Solvay AMPS-EA diblock   1% copolymer (2Da-15 Da), ~30% aqua solution max pressure on 3.2 Ap 3.2 Ap 2.5 Apscreen (Ampere) Granulation 55 RPM 55 RPM 55 RPM speed d90 after 20 μ 20μ 20 μ milling d90 after 20 μ 20 μ 20 μ granulation Granulation 1.2 mm1.2 mm 1.2 mm screen

The three different compositions exemplified in the Table 4 were testedfor granulation of a Pymetrozin-Dinotefuran formulation. Thecompositions and granulation process differ only by the surface activeagents used. Samples 1 and 2 used conventional surfactants atconcentration of 2% while sample 3 used 1% of the PolyAgro A2 polymersolution (˜30% w/w).

During the granulation process the milled powder was pressed through ascreen. The pressure that developed required more electric power to pushthe powder through the screen. The electric current was measured and wasan indication for the pressure. In the case of sample 3, the lowestcurrent was needed in the granulation process indicating the lowestpressure that developed.

That is, the formulations without the present block copolymer had asevere pressure problem which developed during granulation, and whichwas only solved using the present block copolymer. The electricalcurrent needed for the granulator in order to overcome the developedpressure and achieve the necessary granulation speed is given in amperesand indicates the extrusion pressure problem.

Example 5 Polyelectrolyte-Layer Forming Block Copolymer B (PolyAgro B)Formulation

The formulation of an exemplary copolymer according to the presentsubject matter, labeled herein as PolyAgro B, is represented below inTable 5:

TABLE 5 Total STAB ANCHOR AMPS EA AMPS EA Mnth Mnth Mnth DPn DPn (mol %)(mol %) (wt %) (wt %) (g/mol) (g/mol) (g/mol) STAB ANCHOR 69 31 83.316.7 12,000 10,000 2,000 44 20

This is a di-block copolymer, with a total weight of 12000 g/mol,composed of a hydrophobic block (Anchor block—ANCHOR) and a hydrophilicblock (Stabilizing block—STAB). The stabilizing, hydrophilic, block ismade of sodium 2-Acryloylamino-2-methylpropane-1-sulfonate (AMPS)monomers, which are 69% of the overall monomers in the polymer. Theother 31% of the monomers belongs to the anchor, hydrophobic, blockwhich is made of ethyl acrylate monomers. The total amount of monomersin the polymer (degree of polymerization, DPn) is 64 monomers.

This polymer may be obtained according to the following procedure.

a) Macro CTA

Into a 2 L double jacketed reactor equipped with mechanical agitator andreflux condenser was added 14.9 g ofO-ethyl-S-(1-methoxycarbonylethyl)xanthate (CH3CH(CO2CH3))S(C═S)OEt),266.2 g of Ethanol, and 364.7 g of De-ionized water and 1400 g ofAMPS(Na) solution (50% active) and 1.7 g of sodium persulfate. Thereactor contents were heated to 70° C. under agitation and nitrogen. Thereaction mixture was aged at 70° C. for a further hour whereupon it wascooled to ambient temperature and discharged. The measured solidscontent was 38% (115° C., 60 mins).

b) Chain Extension

Into a 2 L double jacketed reactor equipped with mechanical agitator andreflux condenser was added 1314.8 g of macro CTA solution (see a) and283 g of de-ionized water. The reactor content were heated to 70° C.under agitation and nitrogen at 70° C. start add 100 g of ethyl acrylate(EA) over 2 H 00 and 24.8 g of a solution of 12 wt % of sodiumpersulfate over 2 h 30. After the end of the introduction of theinitiator solution, aged for one hour. Add in one shot 14.3 g of asolution 12 wt % of sodium persulfate and aged at 70° C. for a furtherhour whereupon it was cooled to ambient temperature and discharged. Themeasured solids content was 35.4% (115° C., 60 mins).

Ethanol was removed from the polymer solution using a rotary evaporator.Water was back added to achieve a polymer solution with a final solidscontent of 35.8%.

1101 g of stripped polymer solution was placed in a 2 L double jacketedreactor equipped with mechanical agitator and reflux condenser. The pHof the solution was increased to 8.5 using 105 g of a 5 wt %(NaHCO3/Na2CO3 50/50 mol %) buffer solution and 87.8 g of de-ionizedwater. The mixture was heated to 70° C. with stirring whereupon 35.8 gof a 30% solution of hydrogen peroxide was added in 1 hour at the end ofthe additions, the solution was aged for a further 3 h 00 whereupon itwas cooled and discharged.

The measured solids content were 32.2% (PolyAgro B2).

This example provides the results of milling high load suspensionconcentrate formulation with present block copolymeric surfactant(“PolyAgro B”). This formulation with PolyAgro B2, i.e. Formulation 3,is summarized in Table 6 below. The preparation method of Formulation 3is similar to that of Formulation 2 described in Example 2.

Comparison between the viscosities during the milling of the aboveFormulation 3 and Formulation 2 is presented in FIG. 6.

TABLE 6 Formulation 3-with PolyAgro B2 % Total Step 1 Step 2 Step 3Ingredient Supplier w/w (g/L) (g) (g) (g) Folpet 98% Adama Active 71.271033 485.7 331.2 217.0 tech Makhteshim ingredient Atlox ™ 4913 Crodapolymethyl 2.41 35 8.4 10.8 15.5 methacrylate- polyethylene glycol graftcopolymer PolyAgro B2 Solvay AMPS-EA 1.59 23 12.8 6.2 4.0 diblockcopolymer (2 Da-10 Da), ~30% aqua solution Lankropol KO2 AkzoNobelSodium dioctyl 0.53 7.7 3.5 2.4 1.8 sulphosuccinate Water Solvent 20.23293 293 Other 3.94 57 57 ingredients Sum 100.00 1450

Example 6 Oil in Water Pesticidal Composition

In this example, a stable pesticidal formulation of oil in water (o/w)emulsion which is rich in organic phase is presented. The activeingredient is the nematocide Fluensulfone. The composition is presentedin Table 7. The organic phase is added to the aqua phase and then theemulsion is produced using high shear homogenizer. The final dropletsize is D90<2 μm, the final Fluensulfone is 630 gr/l, the organic phasecontent is 69%, which is more than twice than the aqua phase. The finalviscosity, after high shear, is 370 cP (measured at 12 RPM, spindle 62,Brookfield viscometer.).

Example 7 Aqueous Non-Agricultural-Application-Based Composition

Evaluation of the efficacy and optimum use level of the polymer preparedin Example 5 for the preparation of a pigment color pastes wasdetermined by dispersant demand curve studies. Starting pointformulations were chosen for 3 pigments Blue PB 15:2 (40% solids), BlackRaven® 5000 (20% solids) and Yellow PY42 (50% solids). For each specificpigment a demand curve was acquired by obtaining 6 viscosity data pointscorresponding to the dispersion of 6 samples with varying activedispersant to pigment ratios. Each sample contains 1.5 g in total.

In a typical procedure, 6 4-ml-glass vials were loaded with a givenamount of 2-mm-glass beads, then the same quantity of pigment was loadedinto the vial. The amounts of glass beads and particles for Blue PB15:2, Black Raven® 5000 and Yellow PY42 are respectively 600 mg, 300 mgand 750 mg. Thereafter antifoam (20 mg, BYK022), dispersant aqueoussolution, at 20% for Blue PB 15:2, Black Raven® 5000 and 5% for YellowPY42 (adjusted to pH 9-10 with ammonia solution) and DI water (adjustedto pH 9-10 with ammonia) were added. The amount of dispersant added toeach vial was varied such that the active dispersant to pigment ratiowas between 6-21% for PB 15:2, 20-70% for Raven® 5000 and 0.3-4% forPY42. The Di water water amount was added such that the final pigmentconcentrations were 40% for PB 15:2, 20% for Raven® 5000 and 50% forPY42. The mixture was wetted by gentle vortex mixing and then dispersedusing vigorous vortex agitation for 90 min using a Scientific industriesVortex-Genie® 2 speed 6-8. The viscosity of the dispersions in thedifferent vials was measured using a Gilson Viscoman portableviscometer.

The results for the different evaluations are tabulated below in Tables8-10.

TABLE 8 Viscosity Dispersant on Reference Viscosity Pigment PB15:2Solsperse ™ 65000 Example 5 (%) (cps) (cps) 6 1050 220 9 160 9030 12 70200 15 250 370 18 3880 1090 21 4070 1910

TABLE 9 Viscosity Dispersant on Reference Viscosity Pigment RavenSolsperse ™ 65000 Example 5 5000 (%) (cps) (cps) 20 19 40 30 8 19 40 618 50 8 19 60 27 28 70 47 27

TABLE 10 Viscosity Dispersant on Reference Viscosity Pigment PY42Solsperse ™ 65000 Example 5 (%) (cps) (cps) 0.3 >10000 >10000 0.6 >100002840 1 380 660 2 >10000 23 3 260 20 4 >10000 22

They show that low viscosity dispersions may be obtained for allpigments evaluated with the dispersant from Example 5. They also showthe improved universality of the polymer of the invention versus thereference dispersant Solsperse™ 65000.

While the present subject matter has been shown and described withreference to preferred embodiments thereof, it will be understood bythose skilled in the art that many alternatives, modifications andvariations may be made thereto without departing from the spirit andscope thereof. Accordingly, it is intended to embrace all suchalternatives, modifications, and variations that fall within the spiritand broad scope of the appended claims.

The reference in this specification to any prior publication (orinformation derived from it), or to any matter which is known, is not,and should not be taken as an acknowledgment or admission or any form ofsuggestion that that prior publication (or information derived from it)or known matter forms part of the common general knowledge in the fieldof endeavor to which this specification relates.

What is claimed:
 1. An agricultural material, a pesticidal, an aqueousnon-agricultural-application-based, a colorant system, or an oil cementgrout composition comprising: (i) particles of at least one compound;and (ii) a dispersant system comprising a polyelectrolyte-layer formingblock copolymer, wherein the block copolymer comprises (A) an anchoringmoiety and (B) at least one stabilizing moiety, wherein the blockco-polymer is adsorbed on hydrophobic surfaces of the particles. 2.(canceled)
 3. The composition of claim 1, wherein the composition is anagricultural material composition and the compound is an agriculturalmaterial compound selected from a group consisting of a pesticide, aplant growth regulator, a hormone, and a bio-stimulant.
 4. (canceled) 5.(canceled)
 6. The composition of claim 3, wherein the pesticide is aninsecticide, a nematocide, an herbicide, a fungicide, an algicide, ananimal repellent, or an acaricide. 7-11. (canceled)
 12. The compositionof claim 1, wherein: a) the composition is high-load and theconcentration of agricultural material particles in the composition is900-1200 g/L, b) the density of the composition is 1.4-1.6 kg/L, c) theviscosity of the composition is less than 750 cPs when determined atspindle 62 and 12 RPM of Brookfield viscometer, and/or d) thecomposition is stable in a high salt environment. 13-18. (canceled) 19.The composition of claim 1, wherein the composition is an aqueousnon-agricultural-application-based composition comprising at least: (i)one non-agricultural material compound; (ii) water; and (iii) adispersant system comprising a polyelectrolyte-layer forming blockcopolymer, wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety.
 20. (canceled)
 21. (canceled)22. The composition of claim 19, wherein the composition is an oilcement grout composition or a colorant system composition.
 23. Thecomposition of claim 1, wherein: (a) the polyelectrolyte-layer formingblock copolymer is a linear block copolymer, or (b) thepolyelectrolyte-layer forming block copolymer is a comb block copolymer.24. (canceled)
 25. The composition of claim 19, wherein: (a) thepolyelectrolyte-layer forming block copolymer is a linear blockcopolymer, or (b) the polyelectrolyte-layer forming block copolymer is acomb block copolymer.
 26. The composition of claim 1, wherein: (a) theanchoring moiety is a hydrophobic block copolymer, and/or (b) the atleast one stabilizing moiety is a hydrophilic block copolymer.
 27. Thecomposition claim 26, wherein: (a) at least 90% by weight of monomers inthe anchoring moiety is hydrophobic monomers selected from the groupconsisting of acrylate derivatives, methacrylate derivatives, styrenederivatives, and any combination thereof, (b) at least 60% by weight ofmonomers in the stabilizing moiety are charged monomers selected fromanionic monomers having a sulfonate group, and/or (c) less than 40% byweight of the monomers in the stabilizing moiety are neutral hydrophilicmonomers selected from a group consisting of N-vinylpyrrolidone,ethylene oxide, glycoside acrylate, and acrylamide.
 28. (canceled) 29.(canceled)
 30. The composition of claim 19, wherein: (a) the anchoringmoiety is a hydrophobic block copolymer, and/or (b) the at least onestabilizing moiety is a hydrophilic block copolymer.
 31. The compositionof claim 30, wherein: (a) at least 90% by weight of monomers in theanchoring moiety is hydrophobic monomers selected from the groupconsisting of acrylate derivatives, methacrylate derivatives, styrenederivatives, and any combination thereof, (b) at least 60% by weight ofmonomers in the stabilizing moiety are charged monomers selected fromanionic monomers having a sulfonate group, and/or (c) less than 40% byweight of the monomers in the stabilizing moiety are neutral hydrophilicmonomers selected from a group consisting of N-vinylpyrrolidone,ethylene oxide, glycoside acrylate, and acrylamide. 32-36. (canceled)37. The composition of claim 1, wherein: a) the block copolymercomprises up to 150 monomers, b) the weight of the block copolymer is upto 31000 g/mol, c) the weight of the stabilizing moiety is 5,000 to100,000 g/mol, d) the weight of the anchoring moiety is 500 to 5,000g/mol, e) the weight percentage of the stabilizing moiety is 65-90% ofthe total weight of the block copolymer. f) the molar ratio of theanchoring moiety to the stabilizing moiety is 1:2-4, and/or g) theconcentration of the block copolymer in the composition is 0.2-3% w/w.38. A method of (i) controlling and preventing pest or (ii) improvingplant growth comprising applying an agricultural material composition to(a) a locus where the pest is to be controlled and prevented or (b) atleast one of a plant, an area adjacent to a plant, soil adapted tosupport growth of a plant, a root of a plant, foliage of a plant, and/ora seed adapted to produce a plant, wherein the composition comprises:(i) particles of at least one agricultural material compound; and (ii) adispersant system comprising a polyelectrolyte-layer forming blockcopolymer, wherein the block copolymer comprises (A) an anchoring moietyand (B) at least one stabilizing moiety, wherein the block co-polymer isadsorbed on surfaces of the agricultural material compound particles.39-43. (canceled)
 44. A process of preparing a composition comprisingmixing particles of at least one compound with an amount of apolyelectrolyte-layer forming block co-polymer, wherein the blockcopolymer comprises (A) an anchoring moiety and (B) at least onestabilizing moiety.
 45. The process of claim 44, wherein the at leastone compound is an agricultural material compound.
 46. (canceled) 47.(canceled)
 48. The process of claim 44, wherein the at least onecompound is a non-agricultural material compound.
 49. (canceled)
 50. Theprocess of claim 44, wherein mixing comprises preparing a dispersion ofparticles of the at least one compound and adsorbing thepolyelectrolyte-layer forming block copolymer on hydrophobic surfaces ofthe particles to form a polyelectrolyte layer on the particle interface.51. (canceled)
 52. The process of claim 44, wherein: (a) the processfurther comprises a step of wet milling the particles after thepolyelectrolyte layer is formed wherein (i) the amount of the blockcopolymer is effective to reduce temperature during wet milling of thecomposition compared to the temperature during wet milling of the samecomposition without the block co-polymer, and/or (ii) the amount of theblock copolymer is effective to reduce viscosity of the compositionduring wet milling of the composition compared to the viscosity of thesame composition without the block copolymer during wet milling, or (b)the process further comprises a step of granulating the compositionafter the polyelectrolyte layer is formed and wherein the amount of theblock copolymer is effective to reduce pressure during granulation ofthe composition compared the pressure during granulation of the samecomposition without the block copolymer. 53-61. (canceled)
 62. Thecomposition of claim 19, wherein: a) the block copolymer comprises up to150 monomers, b) the weight of the block copolymer is up to 31000 g/mol,c) the weight of the stabilizing moiety is 5,000 to 100,000 g/mol, d)the weight of the anchoring moiety is 500 to 5,000 g/mol, e) the weightpercentage of the stabilizing moiety is 65-90% of the total weight ofthe block copolymer. f) the molar ratio of the anchoring moiety to thestabilizing moiety is 1:2-4, and/or g) the concentration of the blockcopolymer in the composition is 0.2-3% w/w.